Fabrication method for fused multi-layer amorphous selenium sensor

ABSTRACT

A sensor including a layer of amorphous selenium (a-Se) and at least one charge blocking layer is formed by depositing the charge blocking layer over a substrate prior to depositing the amorphous selenium, enabling the charge blocking layer to be formed at elevated temperatures. Such a process is not limited by the crystallization temperature of a-Se, resulting in the formation of an efficient charge blocking layer, which enables improved signal amplification of the resulting device. The sensor can fabricated by forming first and second amorphous selenium layers over separate substrates, and then fusing the a-Se layers at a relatively low temperature.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of co-pending applicationhaving U.S. Ser. No. 16/715,023, filed on Dec. 16, 2019, which is acontinuation of co-pending application having U.S. Ser. No. 15/761,187,filed on Mar. 19, 2018, now U.S. Pat. No. 10,547,015, which is a 371 ofInternational Application having Serial No. PCT/US2017/063857, filed onNov. 30, 2017, which claims the benefit of priority from U.S.Provisional Application No. 62/429,101, filed on Dec. 2, 2016, thecontent of which is incorporated herein by reference in its entirety.

GOVERNMENT LICENSE RIGHTS

This invention was made with government support under grant numberEB002655 awarded by the National Institutes of Health. The governmenthas certain rights in the invention.

BACKGROUND OF THE INVENTION

The present application relates generally to sensors adapted to detectoptical or ionizing radiation, and more specifically to multi-layeramorphous selenium (a-Se) sensors and their methods of production.

Amorphous selenium (a-Se) has been commercialized both as an opticalsensor and direct x-ray detector, and a-Se with avalanche gain has alsobeen proposed for use in an indirect x-ray detector. Advantages of a-Seover other photoconductors such as silicon, which may be used in bothoptical and x-ray sensing applications, and CdTe, which may be used todetect x-rays, include the capability for large area deposition,avalanche multiplication of holes at electric fields (ESe) greater than70 V/um, and monotonically increasing x-ray conversion gain with ESe.

As will be appreciated, conventional x-ray detectors, especially x-raydetectors adapted for low photon flux applications, suffer from imagedegradation due to electronic noise. However, decreasing the electronicnoise of readout electronics increases the cost of the imager and haslimited effect.

On the other hand, for a-Se detectors electronic noise can be overcomeby increasing ESe to amplify the signal prior to the introduction ofelectronic noise. For optical sensors, ESe greater than 70 V/um isrequired for avalanche gain, while for direct x-ray sensors any increasein ESe will increase conversion gain.

SUMMARY OF THE INVENTION

Notwithstanding recent developments, there is a need for improvedmethods for fabricating a-Se-containing structures that can beincorporated into systems for optical and x-ray sensing where signalamplification can be realized prior to the introduction of electronicnoise. As described herein, a-Se-containing structures may be made bydelaying the formation of temperature-sensitive amorphous seleniumlayers until after the elevated temperature processing of chargeblocking layers within the structures.

In accordance with various embodiments, a method of fabricating a sensorincludes forming a first charge blocking layer over a first substrate,forming a first layer of amorphous selenium over the first chargeblocking layer, forming a second charge blocking layer over a secondsubstrate, and forming a second layer of amorphous selenium over thesecond charge blocking layer.

The first layer of amorphous selenium is then brought into contact withthe second layer of amorphous selenium to form a multi-layer structure,which is heated to fuse the first layer of amorphous selenium to thesecond layer of amorphous selenium. Fusion may be accomplished byheating to above the glass transition temperature (T_(g)) of amorphousselenium, but below its crystallization temperature (T_(c)).

According to further embodiments, a sensor-forming method includesforming a charge blocking layer over a substrate, forming a layer ofamorphous selenium over the charge blocking layer, and heating the layerof amorphous selenium to fuse the layer of amorphous selenium to thecharge blocking layer.

BRIEF DESCRIPTION OF SEVERAL VIEWS OF THE DRAWINGS

The following detailed description of specific embodiments of thepresent application can be best understood when read in conjunction withthe following drawings, where like structure is indicated with likereference numerals and in which:

FIG. 1A is a schematic diagram of an optical sensor including a layer ofamorphous selenium;

FIG. 1B is a schematic diagram of a direct x-ray sensor that includes anactive layer of amorphous selenium;

FIG. 1C is a schematic diagram of a combination solid state activematrix flat panel imager (AMFPI) and optical imager that include a layerof amorphous selenium;

FIG. 2A illustrates the sequential formation of a charge blocking layerand a first layer of amorphous selenium over a substrate including anelectronic readout;

FIG. 2B illustrates the formation of a charge blocking layer and asecond layer of amorphous selenium over a substrate;

FIG. 2C shows the formation of a multi-layer structure by the alignmentand subsequent fusion of first and second layers of amorphous seleniumaccording to various embodiments;

FIG. 3A illustrates the sequential formation of a charge blocking layerand a first layer of amorphous selenium having a first thickness over asubstrate including an electronic readout;

FIG. 3B illustrates the formation of a charge blocking layer and asecond layer of amorphous selenium having a second thickness differentfrom the first thickness over a substrate;

FIG. 3C shows the formation of a multi-layer structure by the alignmentand subsequent fusion of first and second layers of amorphous seleniumaccording to certain embodiments;

FIG. 4A shows an example sensor structure formed by the lamination andfusion of separately-formed layers of amorphous selenium;

FIG. 4B shows a further example sensor structure formed by thelamination and fusion of separately-formed layers of amorphous selenium;

FIG. 5 depicts an experimental set-up used to evaluate the disclosedmulti-layer sensors;

FIG. 6 is a plot of time of flight versus electric field for an examplemulti-layer sensor; and

FIG. 7 is a plot of normalized signal versus time demonstrating minimalghosting for an exemplary multi-layer sensor.

DETAILED DESCRIPTION OF THE INVENTION

Reference will now be made in greater detail to various embodiments ofthe subject matter of the present application, some embodiments of whichare illustrated in the accompanying drawings. The same referencenumerals will be used throughout the drawings to refer to the same orsimilar parts.

Schematic diagrams of an example optical sensor, direct x-ray detector,and indirect x-ray detector are shown in FIG. 1A, FIG. 1B and FIG. 1C,respectively.

Referring to FIG. 1A, an optical sensor includes a transparent substrate100 such as an electroded glass substrate. The high voltage electrode(not separately shown) can be formed on the substrate from a suitabletransparent, conductive material such as indium tin oxide (ITO) usingconventional deposition and patterning techniques such as physical vapordeposition (e.g., evaporation or sputtering) and photolithography.

A first charge blocking layer 120 is formed over the substrate 100.First charge blocking layer 120 may be a high temperature, high fieldhole blocking layer formed from an organic polymer, for example. Firstcharge blocking layer 120 may be formed using a thermal or chemicaldeposition process.

Referring still to FIG. 1A, a layer of amorphous selenium (a-Se) 130 isdisposed over the first charge blocking layer 120. In the variousembodiments disclosed herein, a layer of amorphous selenium may have athickness of 0.5 to 100 microns, e.g., 0.5, 1, 2, 4, 8, 10, 20, 50 or100 microns, including ranges between any of the foregoing values. Theamorphous selenium may be doped (stabilized) or un-doped. Exampledopants include arsenic, tellurium and chlorine, which may be includedin amounts of 0.1 to 0.5 atomic percent, e.g., 0.1, 0.2, 0.3, 0.4 or 0.5at. %, including ranges between any of the foregoing values.

A second charge blocking layer 140 is formed over the layer of amorphousselenium 130. In a comparative structure, second charge blocking layer140 may be a low temperature, high field electron blocking layer formedfrom an organic polymer, for example. Second charge blocking layer 140may be formed using a thermal or chemical deposition process. As will beappreciated, a low temperature process for forming the second chargeblocking layer 140 directly over the layer of amorphous selenium (a-Se)130 may be used to avoid crystallization of the underlying seleniumlayer 130. In the present context, “low temperature” means a processtemperature less than a crystallization onset temperature for selenium,e.g., less than 80° C. or less than 60° C.

In the illustrated embodiment, a space 200 such as an air gap or vacuumgap separates the multi-layer structure including substrate 100, firstcharge blocking layer 120, a-Se layer 130, and second charge blockinglayer 140 from readout electronics 160. Readout electronics 160 mayinclude an electron beam readout. Insomuch as the optical avalanchestructure of FIG. 1A relies on a vacuum tube design, the directconversion sensor cannot operate above an ESe of about 10 V/um. Theoptical sensor of FIG. 1A is adapted to receive optical radiation 50through transparent substrate 100. When the a-Se is capable of avalanchegain, the structure is referred to as High Gain Avalanche RushingPhotoconductor (HARP).

Referring to FIG. 1B, shown schematically is an exemplary direct x-raysensor. The direct x-ray sensor includes a layer of amorphous selenium230 disposed between a first charge blocking layer 240 and a secondcharge blocking layer 220. First charge blocking layer 240 may be a hightemperature, low field electron blocking layer, while in a conventionalstructure, second charge blocking layer 220 may be a low temperature,low field hole blocking layer. That is, for thermal compatibility withan already-formed layer of amorphous selenium 230, the second chargeblocking layer 220 may be formed at a low temperature, i.e., less than acrystallization onset temperature for amorphous selenium.

Pixel electrodes 250 may be disposed proximate to readout electronics260. During operation, ionizing radiation such as x-ray radiation 60 mayenter the x-ray sensor of FIG. 1B through a transparent, high-voltage(HV) electrode 210. HV electrode 210 may include a patterned layer ofITO, for example.

Referring to FIG. 1C, shown is a scintillating HARP-AMFPI (left) andoptical imager (right). Each sensor includes, from bottom to top,readout electronics 360, one or more pixel electrodes 350, an electronblocking layer (EBL) 340, a layer of amorphous selenium 330, a holeblocking layer (HBL) 320, and a high voltage electrode 310. During use,optical radiation 50 may enter the optical imager through the HVelectrode 310.

In the illustrated structure, the scintillating HARP-AMFPI sensoradditionally includes a scintillator 305 disposed over the HV electrode310. During use, ionizing radiation 60 may enter the scintillatingHARP-AMFPI sensor through the scintillator 305.

In certain structures, an air gap 300 between the scintillator 305 andthe a-Se layer 330 may lead to spatial blurring and image degradation.The scintillating HARP-AMFPI shown in FIG. 1C, when formed with a lowtemperature (i.e., defect-containing) HBL 320 may exhibit inferiorperformance, such as breakdown during operation.

As will be appreciated, a challenge facing developers of optical andx-ray detectors, such as those described with reference to FIGS. 1A-1C,and including solid-state active matrix flat panel imagers (AMFPI)utilizing an avalanche a-Se sensor, relates to the potential for aprocessing incompatibility between the amorphous selenium layer and thedielectric layer(s) (i.e., charge blocking layers) used to isolate thea-Se and inhibit charge injection, i.e., dark current injection, fromadjacent electrodes during operation.

A difficulty lies in creating a multi-layer structure that can withstandthe high ESe and limit dark current injection from the electrodes. Atypical detector structure, regardless of application geometry or ESerequirements, includes an n-type, hole blocking layer (HBL) and ap-type, electron blocking layer (EBL) to isolate the a-Se from thepositive high voltage (HV) and negatively biased electrodes,respectively, to prevent charge injection.

Desired materials for the charge blocking layers include semiconductingoxides and polymers. Exemplary oxide layers (e.g., silicon dioxide) aretypically formed via physical vapor deposition (PVD) or chemical vapordeposition (CVD) at a substrate temperature of at least 200° C. Polymerlayers, on the other hand, may be deposited by solution-basedprocessing, but typically require an annealing step at elevatedtemperatures (e.g., greater than 60° C.) to remove solvent andcross-link the polymer.

During the fabrication of the comparative detectors shown in FIGS.1A-1C, a charge blocking layer formed over a layer of a-Se must bedeposited at substrate temperature less than the crystallization onsettemperature for amorphous selenium (i.e., about 60° C.) in order toavoid the formation polycrystalline aggregates within the amorphousselenium.

As will be appreciated, semiconducting oxides and polymers that areformed using sub-optimal conditions (i.e., deposition or curingtemperatures of less than about 200° C.) result in poor stoichiometryand the incorporation of defects into the charge blocking layer that maynegatively impact performance or even cause failure, particularly athigh ESe. Thus, the performance of the sensors depicted in FIGS. 1A-1Cmay be limited by the deposition temperature of the top charge blockinglayer.

According to various embodiments, the fabrication of a multi-layersensor architecture, including a layer of amorphous selenium, includesthe formation of a first portion of the amorphous selenium layer over apreviously-formed first charge blocking layer, i.e., an electronblocking layer (EBL), and the formation of a second portion of theamorphous selenium layer over a previously-formed second charge blockinglayer, i.e., a hole blocking layer (HBL). The disclosed process delaysthe formation of the first and second portions of the (temperaturesensitive) amorphous selenium layer until after formation of therespective charge blocking layers. In certain embodiments, the chargeblocking layers are formed on separate substrates. This allows the EBLand HBL deposition processes to be conducted at a relatively hightemperature without adversely affecting the layer(s) amorphous selenium.An example process can be understood with reference to FIGS. 2A-2C.

Referring to FIG. 2A, the fabrication process flow for a fused seleniumsensor according to various embodiments includes the formation of anelectron blocking layer (EBL) 440 over a first substrate 460. The firstsubstrate 460 may include an electronic readout such as a thin filmtransistor, CMOS transistor or photon counting sensor. A pixel electrodeor a pixel electrode array 450 may be disposed over the first substrate460, e.g., between the first substrate 460 and the EBL 440. A firstdoped or un-doped layer of amorphous selenium 431 having a firstthickness (T1) is deposited over the EBL 440.

Separately, referring to FIG. 2B, a hole blocking layer (HBL) 420 isformed over a second substrate 405. The second substrate 405 may includeany substrate suited for the desired application, including ascintillator, fiber optic faceplate, glass, or glass carrier for ade-bonded clear thin polymer. The second substrate 405 may be anelectroded substrate, including a high voltage (HV) electrode 410. TheHV electrode may include indium tin oxide, for example. A second dopedor un-doped layer of amorphous selenium 432 having a second thickness(T2) is then deposited over the HBL 420.

In certain embodiments, the first layer of amorphous selenium 431 andthe second layer of amorphous selenium 432 may each be doped. In certainembodiments, the first layer of amorphous selenium 431 and the secondlayer of amorphous selenium 432 may each be un-doped.

Referring to FIG. 2C, in a further step, the first layer of amorphousselenium 431 is brought into contact with the second layer of amorphousselenium 432 to form a multi-layer structure 400, which is heated at atemperature sufficient to fuse the first layer of amorphous selenium tothe second layer of amorphous selenium. Fusion may be accomplished byheating to above the glass transition temperature (T_(g)) of amorphousselenium, but below its crystallization temperature (T_(c)). The fusiontemperature will be determined by the glass transition temperature,which is dependent on the extent of doping of the amorphous seleniumlayer(s). In certain embodiments, fusion of the first and second layersof amorphous selenium may be accompanied by the application of acompressive force. In certain embodiments, the fusion may be performedin air or under vacuum, e.g., if air cavities inhibit uniform fusion.

Above its glass transition temperature, a-Se becomes a viscus, rubberlike adhesive allowing for two layers of selenium to be fused together.The soft and flexible state will planarize and remove surface topologyin the a-Se, which may result from deposition imperfections or substratetopology. By fusing the first and second layers of amorphous selenium ata temperature than the recrystallization temperature of selenium, theresulting composite (multi-layer) structure 431, 432, which has a totalthickness T=T1+T2, may be free of any crystalline phase(s).

In certain embodiments, one or both substrates may be a flexiblesubstrate. Flexible substrates such as thin glass, phosphor screens andMylar films may induce less stress on the a-Se, resulting in moreuniform fusion over a large area compared to inflexible glasssubstrates, for example.

Applicant has shown that unequal charge transport of holes and electronsacross the fusion interface can be advantageous to device performance.Although T1 is equal to T2 in the illustrated embodiment of FIG. 2C, therespective thicknesses of the first and second layers of amorphousselenium can be varied such that the fusion interface is closer to oneof the blocking layers, which can improve by blocking property of thatblocking layer.

For instance, according to various embodiments, time of flight (TOF)measurements for a single pixel sensor measuring about 2 cm×2 cmdemonstrate that holes, which are the primary charge carrier in a-Se,move across the fusion interface. In such case, if electron transportacross the fusion interface is significantly worse than holes, thethicknesses of the respective a-Se layers can be selected such that T2is greater than T1, whereby poor transport across the fusion interfacecan contribute to electron blocking. The thickness of T1 may bedecreased so long as the substrate topology is planarized and uniformfusion can be achieved.

Thus, referring to FIGS. 3A-3C, according to further embodiments, afirst layer of amorphous selenium 431 has a thickness T1, while a secondlayer of amorphous selenium 432 has a thickness T2, where T1 is lessthan T2. In an example structure formed by the fusion of two separatelayers of amorphous selenium, the thickness (T1) of one layer may be 5to 200% of the thickness (T2) of the other layer, e.g., 5, 10, 20, 50,100, 150 or 200%, including ranges between any of the foregoing values.For instance, a first layer of amorphous selenium and a second layer ofamorphous selenium may each have a thickness of 5.4 microns. In afurther example, a first layer of amorphous selenium may have athickness of 10 microns and a second layer of amorphous selenium mayhave a thickness of 5 microns.

A further method of fabricating a multi-layer sensor includes forming acharge blocking layer over a substrate, forming a layer of amorphousselenium over the previously-deposited charge blocking layer, andheating the layer of amorphous selenium to fuse the layer of amorphousselenium to the charge blocking layer.

Referring to FIG. 4A and FIG. 4B, shown are exemplary sensorarchitectures that may be formed by the fusion of separately deposited(i.e., top and bottom) layers of amorphous selenium. The architecture inFIG. 4A includes an electroded (e.g., indium tin oxide coated) glasssubstrate 660 and an over-formed first layer of amorphous selenium 631that has been fused to a high voltage ITO coated glass substrate 605 viaan indium gallium zinc oxide (IGZO) layer 610, and an over-formed secondlayer of amorphous selenium 632. After forming the foregoing structure,one of the substrates 605, 660 may be removed (e.g., delaminate) ifdesired. An analogous structure, referring to FIG. 4B, includespoly(3,4-ethylenedioxythiophene) (PEDOT) electrodes 650 formed over asurface of the first layer of amorphous selenium 631.

A measurement system 700 for evaluating a multi-layer sensor is shownschematically in FIG. 5. The measurement system 700 includes a powersupply 710, high voltage filter 720, current amplifier 730 andoscilloscope 740. An example current amplifier 730 is a Stanford SR 570amplifier. A multi-layer sensor 400 may be mounted between the powersupply 710 and the oscilloscope 740, and irradiated with a source ofoptical radiation (e.g., 500 ps, 500 nJ laser pulses).

FIG. 6 is a plot of hole time-of-flight (TOF) versus electric field foran example multi-layer sensor confirming that charge traverses the fusedinterface between first and second layers of amorphous selenium. FIG. 7is a plot of normalized signal versus time for an exemplary multi-layersensor under continuous 30 Hz excitation at 30V (˜5 V/micron)demonstrating negligible ghosting, which is a measure of the drop inx-ray sensitivity of the exposed region of the sensor.

According to various embodiments, by depositing the charge blockinglayer(s) prior to depositing amorphous selenium, the charge blockinglayer(s) as well as readout electronics can be fabricated at elevatedtemperatures. Such processing is not limited by the crystallizationtemperature of a-Se, resulting in the formation of efficient chargeblocking layers, which enables improved signal amplification.

The disclosed methods can be used to form solid state sensors, which aremore reliable than vacuum tube-based sensors. Moreover, such sensors canbe fabricated using existing materials and materials depositiontechnologies. In certain embodiments, unequal charge transport acrossthe interface between the fused first and second amorphous seleniumlayers can be advantageous if the interface is located proximate to theblocking layer for the slower charge carrier.

As used herein, the singular forms “a,” “an” and “the” include pluralreferents unless the context clearly dictates otherwise. Thus, forexample, reference to a “photoconductor layer” includes examples havingtwo or more such “photoconductor layers” unless the context clearlyindicates otherwise.

Unless otherwise expressly stated, it is in no way intended that anymethod set forth herein be construed as requiring that its steps beperformed in a specific order. Accordingly, where a method claim doesnot actually recite an order to be followed by its steps or it is nototherwise specifically stated in the claims or descriptions that thesteps are to be limited to a specific order, it is no way intended thatany particular order be inferred. Any recited single or multiple featureor aspect in any one claim can be combined or permuted with any otherrecited feature or aspect in any other claim or claims.

It will be understood that when an element such as a layer, region orsubstrate is referred to as being formed on, deposited on, or disposed“on” or “over” another element, it can be directly on the other elementor intervening elements may also be present. In contrast, when anelement is referred to as being “directly on” or “directly over” anotherelement, no intervening elements are present.

While various features, elements or steps of particular embodiments maybe disclosed using the transitional phrase “comprising,” it is to beunderstood that alternative embodiments, including those that may bedescribed using the transitional phrases “consisting” or “consistingessentially of,” are implied. Thus, for example, implied alternativeembodiments to a photoconductor layer that comprises amorphous seleniuminclude embodiments where a photoconductor layer consists essentially ofamorphous selenium and embodiments where a photoconductor layer consistsof amorphous selenium.

It will be apparent to those skilled in the art that variousmodifications and variations can be made to the present inventionwithout departing from the spirit and scope of the invention. Sincemodifications, combinations, sub-combinations and variations of thedisclosed embodiments incorporating the spirit and substance of theinvention may occur to persons skilled in the art, the invention shouldbe construed to include everything within the scope of the appendedclaims and their equivalents.

1.-18. (canceled)
 19. A method of fabricating a sensor, comprising:forming a first charge blocking layer over a first substrate; forming afirst layer of amorphous selenium over the first charge blocking layer;and heating the first layer of amorphous selenium to fuse the firstlayer of amorphous selenium to the first charge blocking layer.
 20. Themethod of claim 19, wherein the first substrate is a flexible substrate.21. The method of claim 19, wherein the first charge blocking layer isformed by physical vapor deposition or chemical vapor deposition at atemperature of at least 200° C.
 22. The method of claim 19, wherein thefirst layer of amorphous selenium is heated to a temperature between 35°C. and 60° C. to fuse the layer of amorphous selenium to the firstcharge blocking layer.
 23. The method of claim 19, further comprising:forming a second charge blocking layer over a second substrate; forminga second layer of amorphous selenium over the second charge blockinglayer; and forming a multi-layer structure by contacting the first layerof amorphous selenium and the second layer of amorphous selenium,wherein the first layer of amorphous selenium is fused to the secondlayer of amorphous selenium.
 24. The method of claim 23, wherein thefirst charge blocking layer and the second charge blocking layer eachcomprise an organic polymer.
 25. The method of claim 23, wherein thefirst charge blocking layer and the second charge blocking layer areformed by physical vapor deposition, chemical vapor deposition orsolution-based deposition.
 26. The method of claim 19, wherein the firstsubstrate comprises an electronic readout.
 27. The method of claim 19,wherein the first charge blocking layer is formed over a pixelelectrode.
 28. The method of claim 23, wherein a thickness of the firstlayer of amorphous selenium is less than a thickness of the second layerof amorphous selenium.
 29. The method of claim 3, wherein at least oneof the first layer of amorphous selenium and the second layer ofamorphous selenium comprises doped amorphous selenium.
 30. The method ofclaim 23, wherein the second substrate comprises electroded glass or ascintillator.
 31. The method of claim 23, wherein at least one of thefirst substrate and the second substrate is a flexible substrate. 32.The method of claim 3, further comprising forming a high voltageelectrode over the second substrate.
 33. The method of claim 19, whereinthe multi-layer structure is free of pores.
 34. The method of claim 19,wherein the first layer of amorphous selenium is of a thickness between0.5 microns and 100 microns.
 35. The method of claim 19, wherein thefirst layer of amorphous selenium comprises a dopant selected from thegroup consisting of arsenic, tellurium and chlorine.
 36. The sensor ofclaim 35, wherein the dopant is included in amount of 0.1 atomic percentto 0.5 atomic percent.
 37. The method of claim 23, wherein a thicknessof the first layer of amorphous selenium is within 5% to 200% of athickness of the second layer of amorphous selenium.